Characteristics

Physical characteristics

Pieces of hafnium

Hafnium is a shiny, silvery, ductilemetal that is corrosion-resistant and chemically similar to zirconium[6] (due to its having the same number of valence electrons, being in the same group, but also to relativistic effects; the expected expansion of atomic radii from period 5 to 6 is almost exactly cancelled out by the lanthanide contraction). The physical properties of hafnium metal samples are markedly affected by zirconium impurities, especially the nuclear properties, as these two elements are among the most difficult to separate because of their chemical similarity.[6]

A notable physical difference between these metals is their density, with zirconium having about one-half the density of hafnium. The most notable nuclear properties of hafnium are its high thermal neutron-capture cross-section and that the nuclei of several different hafnium isotopes readily absorb two or more neutrons apiece.[6] In contrast with this, zirconium is practically transparent to thermal neutrons, and it is commonly used for the metal components of nuclear reactors – especially the cladding of their nuclear fuel rods.

Chemical characteristics

Hafnium dioxide

Hafnium reacts in air to form a protective film that inhibits further corrosion. The metal is not readily attacked by acids but can be oxidized with halogens or it can be burnt in air. Like its sister metal zirconium, finely divided hafnium can ignite spontaneously in air. The metal is resistant to concentrated alkalis.

The chemistry of hafnium and zirconium is so similar that the two cannot be separated on the basis of differing chemical reactions. The melting points and boiling points of the compounds and the solubility in solvents are the major differences in the chemistry of these twin elements.[7]

Isotopes

At least 34 isotopes of hafnium have been observed, ranging in mass number from 153 to 186.[8][9] The five stable isotopes are in the range of 176 to 180. The radioactive isotopes' half-lives range from only 400 ms for 153Hf,[9] to 2.0 petayears (1015 years) for the most stable one, 174Hf.[8]

Occurrence

Hafnium is estimated to make up about 5.8 ppm of the Earth's upper crust by mass. It does not exist as a free element on Earth, but is found combined in solid solution with zirconium in natural zirconium compounds such as zircon, ZrSiO4, which usually has about 1–4% of the Zr replaced by Hf. Rarely, the Hf/Zr ratio increases during crystallization to give the isostructural mineral hafnon (Hf,Zr)SiO4, with atomic Hf > Zr.[10] An obsolete name for a variety of zircon containing unusually high Hf content is alvite.[11]

Hafnium reserves have been infamously estimated to last under 10 years by one source if the world population increases and demand grows.[13] In reality, since hafnium occurs with zirconium, hafnium can always be a byproduct of zirconium extraction to the extent that the low demand requires.

Production

Melted tip of a hafnium consumable electrode used in an electron beamremelting furnace, a 1 cm cube, and an oxidized hafnium electron beam-remelted ingot (left to right)

Zirconium is a good nuclear fuel-rod cladding metal, with the desirable properties of a very low neutron capture cross-section and good chemical stability at high temperatures. However, because of hafnium's neutron-absorbing properties, hafnium impurities in zirconium would cause it to be far less useful for nuclear-reactor applications. Thus, a nearly complete separation of zirconium and hafnium is necessary for their use in nuclear power. The production of hafnium-free zirconium is the main source for hafnium.[6]

The chemical properties of hafnium and zirconium are nearly identical, which makes the two difficult to separate.[15] The methods first used — fractional crystallization of ammonium fluoride salts[16] or the fractional distillation of the chloride[17] — have not proven suitable for an industrial-scale production. After zirconium was chosen as material for nuclear reactor programs in the 1940s, a separation method had to be developed. Liquid-liquid extraction processes with a wide variety of solvents were developed and are still used for the production of hafnium.[18] About half of all hafnium metal manufactured is produced as a by-product of zirconium refinement. The end product of the separation is hafnium(IV) chloride.[19] The purified hafnium(IV) chloride is converted to the metal by reduction with magnesium or sodium, as in the Kroll process.[20]

HfCl4 + 2 Mg (1100 °C) → 2 MgCl2 + Hf

Further purification is effected by a chemical transport reaction developed by Arkel and de Boer: In a closed vessel, hafnium reacts with iodine at temperatures of 500 °C, forming hafnium(IV) iodide; at a tungsten filament of 1700 °C the reverse reaction happens, and the iodine and hafnium are set free. The hafnium forms a solid coating at the tungsten filament, and the iodine can react with additional hafnium, resulting in a steady turn over.[7][21]

Hf + 2 I2 (500 °C) → HfI4

HfI4 (1700 °C) → Hf + 2 I2

Chemical compounds

Due to the lanthanide contraction the ionic radii of hafnium(IV) (0.78 angstroms) is almost the same as that of zirconium(IV) (0.79 angstroms).[22] Consequently, compounds of hafnium(IV) and zirconium(IV) have very similar chemical and physical properties.[22] Hafnium and zirconium tend to occur together in nature and the similarity of their ionic radii makes their chemical separation rather difficult. Hafnium tends to form inorganic compounds in the oxidation state of +4. Halogens react with it to form hafnium tetrahalides.[22] At higher temperatures, hafnium reacts with oxygen, nitrogen, carbon, boron, sulfur, and silicon.[22] Some compounds of hafnium in lower oxidation states are known.[23]

Hafnium(IV) chloride and hafnium(IV) iodide have some applications in the production and purification of hafnium metal. They are volatile solids with polymeric structures.[7] These tetrachlorides are precursors to various organohafnium compounds such as hafnocene dichloride and tetrabenzylhafnium.

The white hafnium oxide (HfO2), with a melting point of 2812 °C and a boiling point of roughly 5100 °C, is very similar to zirconia, but slightly more basic.[7]Hafnium carbide is the most refractorybinary compound known, with a melting point over 3890 °C, and hafnium nitride is the most refractory of all known metal nitrides, with a melting point of 3310 °C.[22] This has led to proposals that hafnium or its carbides might be useful as construction materials that are subjected to very high temperatures. The mixed carbide tantalum hafnium carbide (Ta4HfC5) possesses the highest melting point of any currently known compound, 4215 °C.[24] Recent supercomputer simulations suggest a hafnium alloy with a melting point of 4400 K.[25]

History

Photographic recording of the characteristic X-ray emission lines of some elements

In his report on The Periodic Law of the Chemical Elements, in 1869, Dmitri Mendeleev had implicitly predicted the existence of a heavier analog of titanium and zirconium. At the time of his formulation in 1871, Mendeleev believed that the elements were ordered by their atomic masses and placed lanthanum (element 57) in the spot below zirconium. The exact placement of the elements and the location of missing elements was done by determining the specific weight of the elements and comparing the chemical and physical properties.[26]

The discovery of the gaps led to an extensive search for the missing elements. In 1914, several people claimed the discovery after Henry Moseley predicted the gap in the periodic table for the then-undiscovered element 72.[28]Georges Urbain asserted that he found element 72 in the rare earth elements in 1907 and published his results on celtium in 1911.[29] Neither the spectra nor the chemical behavior he claimed matched with the element found later, and therefore his claim was turned down after a long-standing controversy.[30] The controversy was partly because the chemists favored the chemical techniques which led to the discovery of celtium, while the physicists relied on the use of the new X-ray spectroscopy method that proved that the substances discovered by Urbain did not contain element 72.[30] By early 1923, several physicists and chemists such as Niels Bohr[31] and Charles R. Bury[32] suggested that element 72 should resemble zirconium and therefore was not part of the rare earth elements group. These suggestions were based on Bohr's theories of the atom, the X-ray spectroscopy of Moseley, and the chemical arguments of Friedrich Paneth.[33][34]

Encouraged by these suggestions and by the reappearance in 1922 of Urbain's claims that element 72 was a rare earth element discovered in 1911, Dirk Coster and Georg von Hevesy were motivated to search for the new element in zirconium ores.[35] Hafnium was discovered by the two in 1923 in Copenhagen, Denmark, validating the original 1869 prediction of Mendeleev.[36][37] It was ultimately found in zircon in Norway through X-ray spectroscopy analysis.[38] The place where the discovery took place led to the element being named for the Latin name for "Copenhagen", Hafnia, the home town of Niels Bohr.[39] Today, the Faculty of Science of the University of Copenhagen uses in its seal a stylized image of the hafnium atom.[40]

Hafnium was separated from zirconium through repeated recrystallization of the double ammonium or potassium fluorides by Valdemar Thal Jantzen and von Hevesey.[16]Anton Eduard van Arkel and Jan Hendrik de Boer were the first to prepare metallic hafnium by passing hafnium tetraiodide vapor over a heated tungsten filament in 1924.[17][21] This process for differential purification of zirconium and hafnium is still in use today.[6]

In 1923, four predicted elements were still missing from the periodic table: 43 (technetium) and 61 (promethium) are radioactive elements and are only present in trace amounts in the environment,[41] thus making elements 75 (rhenium) and 72 (hafnium) the last two unknown non-radioactive elements. Since rhenium was discovered in 1908, hafnium was the last element with stable isotopes to be discovered.

Applications

Several details contribute to the fact that there are only a few technical uses for hafnium: First, the close similarity between hafnium and zirconium makes it possible to use zirconium for most of the applications; second, hafnium was first available as pure metal after the use in the nuclear industry for hafnium-free zirconium in the late 1950s. Furthermore, the low abundance and difficult separation techniques necessary make it a scarce commodity.[6] When the demand for zirconium dropped following the Fukushima disaster, the price of hafnium increased sharply from around $500–600/kg in 2014 to around $1000/kg in 2015.[42]

Nuclear reactors

The nuclei of several hafnium isotopes can each absorb multiple neutrons. This makes hafnium a good material for use in the control rods for nuclear reactors. Its neutron-capture cross-section is about 600 times that of zirconium. (Other elements that are good neutron-absorbers for control rods are cadmium and boron.) Excellent mechanical properties and exceptional corrosion-resistance properties allow its use in the harsh environment of pressurized water reactors.[18] The German research reactor FRM II uses hafnium as a neutron absorber.[43] It is also common in military reactors, particularly in US naval reactors,[44] but seldom found in civilian ones, the first core of the Shippingport Atomic Power Station (a conversion of a naval reactor) being a notable exception.[45]

Small additions of hafnium increase the adherence of protective oxide scales on nickel-based alloys. It improves thereby the corrosion resistance especially under cyclic temperature conditions that tend to break oxide scales by inducing thermal stresses between the bulk material and the oxide layer.[47][48][49]

In most geologic materials, zircon is the dominant host of hafnium (>10,000 ppm) and is often the focus of hafnium studies in geology.[58] Hafnium is readily substituted into the zircon crystal lattice, and is therefore very resistant to hafnium mobility and contamination. Zircon also has an extremely low Lu/Hf ratio, making any correction for initial lutetium minimal. Although the Lu/Hf system can be used to calculate a "model age", i.e. the time at which it was derived from a given isotopic reservoir such as the depleted mantle, these "ages" do not carry the same geologic significance as do other geochronological techniques as the results often yield isotopic mixtures and thus provide an average age of the material from which it was derived.

Garnet is another mineral that contains appreciable amounts of hafnium to act as a geochronometer. The high and variable Lu/Hf ratios found in garnet make it useful for dating metamorphic events.[59]

Other uses

Due to its heat resistance and its affinity to oxygen and nitrogen, hafnium is a good scavenger for oxygen and nitrogen in gas-filled and incandescent lamps. Hafnium is also used as the electrode in plasma cutting because of its ability to shed electrons into air.[60]

The high energy content of 178m2Hf was the concern of a DARPA-funded program in the US. This program determined that the possibility of using a nuclear isomer of hafnium (the above-mentioned 178m2Hf) to construct high-yield weapons with X-ray triggering mechanisms—an application of induced gamma emission—was infeasible because of its expense. See Hafnium controversy.

Precautions

Care needs to be taken when machining hafnium because it is pyrophoric—fine particles can spontaneously combust when exposed to air. Compounds that contain this metal are rarely encountered by most people. The pure metal is not considered toxic, but hafnium compounds should be handled as if they were toxic because the ionic forms of metals are normally at greatest risk for toxicity, and limited animal testing has been done for hafnium compounds.[61]

Control rods are used in nuclear reactors to control the fission rate of uranium and plutonium. They are composed of chemical elements such as boron, silver, indium and cadmium that are capable of absorbing many neutrons without themselves fissioning. Because these elements have different capture cross sections for neutrons of varying energies, the composition of the control rods must be designed for the reactor's neutron spectrum. Boiling water reactors (BWR), pressurized water reactors (PWR) and heavy water reactors (HWR) operate with thermal neutrons, while breeder reactors operate with fast neutrons.

It contains the elements titanium (Ti), zirconium (Zr), hafnium (Hf) and rutherfordium (Rf). This group lies in the d-block of the periodic table. The group itself has not acquired a trivial name; it belongs to the broader grouping of the transition metals.

The three Group 4 elements that occur naturally are titanium, zirconium and hafnium. The first three members of the group share similar properties; all three are hard refractory metals under standard conditions. However, the fourth element rutherfordium (Rf), has been synthesized in the laboratory; none of its isotopes have been found occurring in nature. All isotopes of rutherfordium are radioactive. So far, no experiments in a supercollider have been conducted to synthesize the next member of the group, unpentoctium (Upo, element 158), and it is unlikely that they will be synthesized in the near future.

Hafnium carbide (HfC) is a chemical compound of hafnium and carbon. With a melting point of about 3900 °C it is one of the most refractory binary compounds known. However, it has a low oxidation resistance, with the oxidation starting at temperatures as low as 430 °C.Hafnium carbide is usually carbon deficient and therefore its composition is often expressed as HfCx (x = 0.5 to 1.0). It has a cubic (rock-salt) crystal structure at any value of x.Hafnium carbide powder is obtained by the reduction of hafnium(IV) oxide with carbon at 1800 to 2000 °C. A long processing time is required to remove all oxygen. Alternatively, high-purity HfC coatings can be obtained by chemical vapor deposition from a gas mixture of methane, hydrogen, and vaporized hafnium(IV) chloride. Because of the technical complexity and high cost of the synthesis, HfC has a very limited use, despite its favorable properties such as high hardness (>9 Mohs) and melting point.The magnetic properties of HfCx change from paramagnetic for x ≤ 0.8 to diamagnetic at larger x. An inverse behavior (dia-paramagnetic transition with increasing x) is observed for TaCx, despite its having the same crystal structure as HfCx.

The hafnium controversy is a debate over the possibility of 'triggering' rapid energy releases, via gamma ray emission, from a nuclear isomer of hafnium, 178m2Hf. The energy release is potentially 5 orders of magnitude (100,000 times) more energetic than a chemical reaction, but 2 orders of magnitude less than a nuclear fission reaction. In 1998, a group led by Carl Collins of the University of Texas at Dallas reported having successfully initiated such a trigger. Signal-to-noise ratios were small in those first experiments, and to date no other group has been able to duplicate these results. Peter Zimmerman described claims of weaponization potential as having been based on "very bad science".

Hafnium diboride belong to the class of Ultra-high-temperature ceramics, a type of ceramic composed of hafnium and boron. It has a melting temperature of about 3250 degrees Celsius. It is an unusual ceramic, having relatively high thermal and electrical conductivities, properties it shares with isostructural titanium diboride and zirconium diboride. It is a grey, metallic looking material. Hafnium diboride has a hexagonal crystal structure, a molar mass of 200.11 grams per mole, and a density of 10.5 grams per cubic centimeter.

Hafnium diboride is often combined with carbon, boron, silicon, silicon carbide, and/or nickel to improve the consolidation of the hafnium diboride powder (sintering). It is commonly formed into a solid by a process called hot pressing, where the powders are pressed together using both heat and pressure.

The material has potential for use in hypervelocity reentry vehicles such as ICBM heat shields or aerodynamic leading-edges, due to its strength and thermal properties. Unlike polymer and composite material, HfB2 can be formed into aerodynamic shapes that will not ablate during reentry.

Hafnium diboride is also investigated as a possible new material for nuclear reactor control rods.

It is also being investigated as a microchip diffusion barrier. If synthesized correctly, the barrier can be less than 7 nm thick.

Hafnium(IV) oxide is the inorganic compound with the formula HfO2. Also known as hafnia, this colourless solid is one of the most common and stable compounds of hafnium. It is an electrical insulator with a band gap of 5.3~5.7 eV. Hafnium dioxide is an intermediate in some processes that give hafnium metal.

Hafnium(IV) oxide is quite inert. It reacts with strong acids such as concentrated sulfuric acid and with strong bases. It dissolves slowly in hydrofluoric acid to give fluorohafnate anions. At elevated temperatures, it reacts with chlorine in the presence of graphite or carbon tetrachloride to give hafnium tetrachloride.

Hafnium disulfide is an inorganic compound of hafnium and sulfur. It is a layered dichalcogenide with the chemical formula is HfS2. A few atomic layers of this material can be exfoliated using the standard Scotch Tape technique (see graphene) and used for the fabrication of a field-effect transistor. High-yield synthesis of HfS2 has also been demonstrated using liquid phase exfoliation, resulting in the production of stable few-layer HfS2 flakes. Hafnium disulfide powder can be produced by reacting hydrogen sulfide and hafnium oxides at 500–1300 °C.

Hafnium tetrabromide is the inorganic compound with the formula HfBr4. It is the most common bromide of hafnium. It is a colorless, diamagnetic moisture sensitive solid that sublimes in vacuum. It adopts a structure very similar to that of zirconium tetrabromide, featuring tetrahedral Hf centers, in contrast to the polymeric nature of hafnium tetrachloride.

Hafnium(IV) chloride is the inorganic compound with the formula HfCl4. This colourless solid is the precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, mainly in materials science and as a catalyst.

Hafnium tetraiodide is the inorganic compound with the formula HfI4. It is a red-orange, moisture sensitive, sublimable solid that is produced by heating a mixture of hafnium with excess iodine. It is an intermediate in the crystal bar process for producing hafnium metal.

In this compound, the hafnium centers adopt octahedral coordination geometry. Like most binary metal halides, the compound is a polymeric. It is one-dimensional polymer consisting of chains of edge-shared bioctahedral Hf2I8 subunits, similar to the motif adopted by HfCl4. The nonbridging iodide ligands have shorter bonds to Hf than the bridging iodide ligands.

Natural hafnium (72Hf) consists of five stable isotopes (176Hf, 177Hf, 178Hf, 179Hf, and 180Hf) and one very long-lived radioisotope, 174Hf, with a half-life of 2×1015 years. In addition, there are 30 other known radionuclides, the most stable of which is 182Hf with a half-life of 8.9×106 years. No other radioisotope has a half-life over 1.87 years. Most isotopes have half-lives under 1 minute. There are also 26 known nuclear isomers, the most stable of which is 178m2Hf with a half-life of 31 years.

According to the giant impact hypothesis a large amount of energy was liberated in the formation of the Moon and it is inferred that as a result a large portion of the Moon was once completely molten, forming a lunar magma ocean. Evidence for the magma ocean hypothesis comes from the highly anorthositic compositions of the crust in the lunar highlands, as well as the existence of rocks with a high concentration of the geochemical component referred to as KREEP.

Ages of formation and crystallization of the lunar magma ocean have been constrained by studies of isotopes of hafnium, tungsten, samarium, and neodymium. The magma ocean formed about 70 million years after the history of the Solar System began, and most of the ocean had crystallized by about 215 million years after that beginning (Brandon, 2007).

Lutetium–hafnium dating is a geochronological dating method utilizing the radioactive decay system of lutetium–176 to hafnium–176. With a commonly accepted half-life of 37.1 billion years, the long-living Lu–Hf decay pair survives through geological time scales, thus is useful in geological studies. Due to chemical properties of the two elements, namely their valences and ionic radii, Lu is usually found in trace amount in rare-earth element loving minerals, such as garnet and phosphates, while Hf is usually found in trace amount in zirconium-rich minerals, such as zircon, baddeleyite and zirkelite.The trace concentration of the Lu and Hf in earth materials posed some technological difficulties in using Lu–Hf dating extensively in the 1980s. With the use of inductively coupled plasma mass spectrometry (ICP–MS) with multi-collector (also known as MC–ICP–MS) in later years, the dating method is made applicable to date diverse earth materials. The Lu–Hf system is now a common tool in geological studies such as igneous and metamorphic rock petrogenesis, early earth mantle-crust differentiation, and provenance.

Neutron capture is a nuclear reaction in which an atomic nucleus and one or more neutrons collide and merge to form a heavier nucleus. Since neutrons have no electric charge, they can enter a nucleus more easily than positively charged protons, which are repelled electrostatically.Neutron capture plays an important role in the cosmic nucleosynthesis of heavy elements. In stars it can proceed in two ways: as a rapid (r-process) or a slow process (s-process). Nuclei of masses greater than 56 cannot be formed by thermonuclear reactions (i.e. by nuclear fusion), but can be formed by neutron capture.

Neutron capture on protons yields a line at 2.223 MeV, predicted and commonly observed

Rutherfordium is a synthetic chemical element with symbol Rf and atomic number 104, named after physicist Ernest Rutherford. As a synthetic element, it is not found in nature and can only be created in a laboratory. It is radioactive; the most stable known isotope, 267Rf, has a half-life of approximately 1.3 hours.

In the periodic table of the elements, it is a d-block element and the second of the fourth-row transition elements. It is a member of the 7th period and belongs to the group 4 elements. Chemistry experiments have confirmed that rutherfordium behaves as the heavier homologue to hafnium in group 4. The chemical properties of rutherfordium are characterized only partly. They compare well with the chemistry of the other group 4 elements, even though some calculations had indicated that the element might show significantly different properties due to relativistic effects.

In the 1960s, small amounts of rutherfordium were produced in the Joint Institute for Nuclear Research in the former Soviet Union and at Lawrence Berkeley National Laboratory in California. The priority of the discovery and therefore the naming of the element was disputed between Soviet and American scientists, and it was not until 1997 that International Union of Pure and Applied Chemistry (IUPAC) established rutherfordium as the official name for the element.

Tantalum hafnium carbide is a refractory chemical compound with a general formula TaxHfy-xCy, which can be considered as a solid solution of tantalum carbide and hafnium carbide. Individually, these two carbides have the highest melting points among the binary compounds, 4,150 K (3,880 °C; 7,010 °F) and 4,201 K (3,928 °C; 7,102 °F), respectively, and their "alloy" with a composition Ta4HfC5 is believed to have a melting point of 4,263 K (3,990 °C; 7,214 °F).Very few measurements of melting point in tantalum hafnium carbide have been reported, because of the obvious experimental difficulties at extreme temperatures. A 1965 study of the TaC-HfC solid solutions at temperatures 2225–2275 °C found a minimum in the vaporization rate and thus maximum in the thermal stability for Ta4HfC5. This rate was comparable to that of tungsten and was weakly dependent on the initial density of the samples, which were sintered from TaC-HfC powder mixtures, also at 2225–2275 °C. In a separate study, Ta4HfC5 was found to have the minimum oxidation rate among the TaC-HfC solid solutions. Ta4HfC5 was manufactured by Goodfellow company as a 45 µm powder at a price of $9,540/kg (99.0% purity).Individual tantalum and hafnium carbides have a rocksalt cubic lattice structure. They are usually carbon deficient and have nominal formulas TaCx and HfCx, with x = 0.7–1.0 for Ta and x = 0.56–1.0 for Hf. The same structure is also observed for at least some of their solid solutions. The density calculated from X-ray diffraction data is 13.6 g/cm3 for Ta0.5Hf0.5C. Hexagonal NiAs-type structure (space group P63/mmc, No. 194, Pearson symbol hP4) with a density of 14.76 g/cm3 was reported for Ta0.9Hf0.1C0.5.In 2015 atomistic simulations predicted that a Hf-C-N material could have a melting point exceeding Ta4HfC5 by 200 K. This has yet to be verified by experimental evidence.

Zirconium is a chemical element with symbol Zr and atomic number 40. The name zirconium is taken from the name of the mineral zircon (the word is related to Persian zargun (zircon;zar-gun, "gold-like" or "as gold")), the most important source of zirconium. It is a lustrous, grey-white, strong transition metal that closely resembles hafnium and, to a lesser extent, titanium. Zirconium is mainly used as a refractory and opacifier, although small amounts are used as an alloying agent for its strong resistance to corrosion. Zirconium forms a variety of inorganic and organometallic compounds such as zirconium dioxide and zirconocene dichloride, respectively. Five isotopes occur naturally, three of which are stable. Zirconium compounds have no known biological role.

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